Diazotype material



United States Patent 3,498,790 DIAZOTYPE MATERIAL Oskar Siis,Wiesbaden-Biebrich, and Heinz Schiifer, Wiesbaden-Sonnenberg, Germany,assignors to Keuifel & Esser Company, Morristown, NJ.

No Drawing. Filed May 5, 1966, Ser. No. 547,799 Claims priority,application Germany, May 8, 1965, K 56,062 Int. Cl. G03c 1/58, 5/22,5/34 US. Cl. 96-91 14 Claims ABSTRACT OF THE DISCLOSURE The presentinvention relates to diazotype material and more particularly tolight-sensitive diazonium compounds useful in the preparation ofdiazotype compositions.

It is known to use, for the preparation of lightsensitive diazotypematerial, i.e. material for photocopying processes which comprises acoating support, for example paper, and a reproduction coating adheringthereto, sensitising mixtures which contain as lightsensitive substancesunilaterally diazotised p-phenylenediamine derivatives. Aslight-sensitive substances in such diazotype sensitising mixtures, greatpractical importance has been attained by diazo compounds which arederived from p-phenylenediamine and in which the amino group inpara-position to the diazo group is tertiary. The essential suitabilityof the p-aminobenzenediazo compounds concerned for the preparation ofso-called two-component material for the dry-development process, or ofsocalled one-component material for the semi-wet development process, isdetermined in each case by the nature of the substituents which may beadhering directly to the benzene ring or to the nitrogen of the tertiaryamino group.

For the preparation of one-component diazotype material, thosesensitising mixtures are well suited which contain p-aminobenzenediazocompounds with a tertiary amino group which are substituted on thetertiary nitrogen atom by an aralkyl radical, for example (andpreferably) the benzyl radical. The presence of the aralkyl group in thediazo compound increases its coupling energy quite substantiallycompared with the coupling energy of a diazo compound with a purelyaliphatic alkyl group instead of the aralkyl radical. The colourdeepening which shows in photocopies prepared from one-componentmaterial sensitised with such diazo compounds is also attributable tothe presence of the aralkyl group in the tertiary aminobenzenediazocompound. For the preparation of black copies by the diazotype process,material sensitized with l-N-(benzylethyl)-amino-4-di azobenzene istherefore used which, after exposure under the original, is treated withdeveloper which is soluble in alkalis and contains phloroglucinol.

As is known, the above-mentioned behaviour in respect of increasedcoupling speed and colour deepening shows still more strongly inone-component material whose light-sensitive coating contains tertiaryp-aminobenzenediazo compounds in which the aralkyl radical on thetertiary nitrogen atom is replaced by a phenoxyalkyl 3,498,790 PatentedMar. 3, 1970 radical. If these diazo compounds substituted by aphenoxyalkyl radical in the tertiary amino group also bear on thebenzene nucleus substituents such as an alkyl or alkoxy radical or ahalogen atom, their water-solu bility in sensitising mixtures, which, asis known, contain stabilisers, e.g. salts of metals, such as zincchloride, or of naphthalenepolysulphonic acids, is greatly reduced. Thekeeping qualities of the sensitising mixtures suffer and, as a result ofturbidity and resin-like precipitates, their suitability for theformation of the light-sensitive coating on the coating support alsosuffers. The objects of the invention are to provide improved diazotypematerial and to provide improved sensitising compositions suitable forthe preparation of diazotype material which are free from thedisadvantages explained above.

According to the present invention diazotype material is provided whichcomprises, as light-sensitive component, a diazo compound having thegeneral formula:

wherein:

R is a hydroxyalkyl radical containing 2 to 4 carbon atoms;

R is an aryloxyalkyl or aryl thioalkyl radical in which the aromaticcomponent may also be substituted;

R is a hydrogen atom or an alkyl or alkoxy or betahydroxyalkoxy group;

R is a hydrogen or halogen atom or an alkyl or alkoxy group; and X is anacid anion.

For the p-aminobenzenediazo compounds with tertiary amino group whichconform to the general formula stated and which characterise thesensitising mixtures according to the invention, the hydroxyalkylradical adhering on the nitrogen of the amino group is characteristic.Compared with the tertiary p-aminobenzenediazo compounds previouslymentioned, they are at least equal to these in respect oflight-sensitivity, coupling speed and tinctorial power, but in respectof water-solubility, particularl in combination with the stabilisersusual in diazotype sensitising mixtures, are substantially superior. Thesensitising mixtures according to the invention therefore permit theaddition of stabilisers in such large amounts that the shelf life of theone-component material sensitised with them is excellent, even undertropical conditions.

A further substantial advance based on the invention is to be seen inthe fact that the dyes which are formed on the photocopies prepared fromthe diazotype material prepared with the sensitising mixtures accordingto the invention are substantially more insensitive to changes inpH-value and therefore have a much lesser tendency to change of colour.The photocopies which are prepared with the use of the one-componentmaterial prepared with the sensitising mixtures according to theinvention can be developed with alkaline solutions or, if the benzenenucleus of the diazo compound according to the invention which ispresent as lightsensitive substance bears substituents which acceleratecoupling, also with a neutral or acid solution.

It may be advantageous to also add to the sensitising mixtures accordingto the invention diazo compounds which are already in use for thesensitising of one-component diazotype material. The coating supports onwhich the light-sensitive coating is formed with the sensitisingmixtures according to the invention are the 3 ;supports with ahydrophilic surface which are commonly .used in diazotype processes.

The diazo compounds according to the above general formula whichcharacterise the sensitising mixtures according to the invention arenew. They are obtained according to known methods. In the table, theformulae of some representatives of these compounds are set forth asexamples. Their preparation is described below.

PREPARATION OF THE COMPOUND OF FORMULA (I) 160.75 g. ofl-N-(beta-hydroxyethyl-beta-phenoxyethyl)-amino-2-methoxy-5-chlorobenzeneare dissolved in 1130 ccm. of 34% sulphuric acid. To this solution areadded dropwise, at an initial temperature of 26 C., 20.8 ccm. of nitricacid (1.52). Towards the end of the dropwise addition, at 36 C. thenitro compound which is formed begins to crystallise out as sulphuricacid salt. As the temperature falls, the reaction mixture is stirred,then filtered with suction and well expressed under a press. Thesulphate tends to split hydrolytically in the presence of water. Thepress cake is dissolved in about 1 litre of methanol (yellowish-redsolution) and the solution rendered neutral with about caustic sodasolution, with good stirring. Filtering with suction is effected fromthe precipitated salt, the salt is washed with a little methanol andRaney nickel is added to the weakly alkaline solution (pH 8). Reductionproceeds at between 20 and 40 C. The initially colourless amine solutionis freed from nickel and to the1-N-(beta-hydroxyethyl-beta-phenoxyethyl)-amino-2-methoxy-4-amino-S-chlorobenzene there are immediately added 150ccm. of fluoroboric acid (35'38% The solvent is evaporated in vacuo. Athick, brownish syrup remains behind. This is dissolved in 1.5 litres offluoboric acid (35-38%) and the solution, heated to about C., isfiltered over 20 g. of animal charcoal. After the addition of 500 ccm.of water, the solution is again filtered over 20 g. of animal charcoalto be then diazotised. Diazotisation is effected by slowly addingdropwise 64 ccm. of 40% solution of sodium nitrite. By rubbing on theglass wall of the diazotisation vessel there is achieved the immediatesolidification in crystalline form of the initially oily diazo compound.To keep the diazotisation mixture stirrable, 1 litre of water is addedto it, stirring is continued for 1-2 hours, and the crystal massfiltered with suction and dried. The crude yield is about 150 g.=% ofthe theory, calculated on the tertiary base. Purification is effected bydissolving 50 g. in ccm. of preheated isopropanol, adding 5 5 0 ccm. ofwater of 8085 C. to the solution and filtering the mixture at 7075 C.over 10 g. of animal charcoal. Melting point: 116 C., withdecomposition.

PREPARATION OF THE COMPOUND OF FORMULA (II):

13.4 g. of l-N-(beta-hydroxyethyl-beta-phenoxyethyl)-amino-Z-ethoxy-S-chlorobenzene are dissolved in ccm. of 34% sulphuricacid and to this solution 1.84 ccm. of

nitric acid (1.52) are added dropwise at room temperature. Thetemperature rises to 32 C. The nitro compound (sulphuric acid salt)which separates out of the solution in the form of yellow drops of oilis separated from the aqueous liquid. From this the free base isobtained by treatment with n-solution of caustic soda. The nitrocompound is now reduced catalytically with Raney nickel in methanolicsolution. After reduction the solution, which contains oxidisablel-N-(beta-hydroxyethylbeta-phenoxyethyl)-amino-2-ethoxy-4-amino 5chlorobenzene, is filtered off from the nickel and 150 ccm. of fluoboricacid (35-38%) and 50 ccm. of water are immediately added to it. Themethanol is distilled off and the remaining amine solution filteredtwice over animal charcoal and then diazotised by the dropwise additonof 5 ccm. of 40% solution of sodium nitrite. When rubbed, the oily,yellow diazo compound solidifies in crystalline form. After filteringwith suction, the crude product is, in order to purify it,recrystallised from a little isopropanol with the addition of water andin this way yellow, long matted needles of the diazo compound areobtained with a melting point of 116 C., with decomposition. Yield: g.

PREPARATION OF THE COMPOUND OF FORMULA (III):

18 g. of l-N-(beta-hydroxyethyl-beta-phenoxyethyl)-amino-2-hydroxyethoxy-5-chlorobenzene are dissolved in 130 com. of 34%sulphuric acid and to this solution 2.36 ccm. of nitric acid (1.52) areadded dropwise at room temperature. The temperature rises slowly to 32C. When water is added to the yellow solution the nitro compoundseparates as a yellow, greasy mass which becomes crystalline whenrubbed. For purification, the crude product is dissolved in chloroformand reprecipitated by adding petroleum ether. Yellow crystals with amelting point of 103-104 C. are obtained. Yield: g.

12 g. of the nitro compound, dissolved in 200 ccm. of methanol, arereduced catalytically by means of Raney nickel. To the solution,filtered off from the nickel, are added 150 ccm. of fluoboric acid(35-38% The methanol is distilled off, the amine solution filtered overanimal charcoal and, for diazotisation, 15 ccm. of 2 N solution ofsodium nitrite are added to it dropwise. The diazo compound froml-N-(beta-hydroxyethyl-beta-phenoxyethyl)-amino-2-hydroxyethoxy-4-amino-5 chlorobenzene forms yellow crystals,which are filtered with suction and, for purification, recrystallisedfrom about 200 ccm. of water at 60 C. Yield: 10 g. Melting point: 107l08C., with decomposition.

PREPARATION OF THE COMPOUND OF FORMULA (IV):

30 g. of l-N-(beta-hydroxyethyl-beta-phenoxyethyl)-amino-2-methoxybenzene are dissolved in 300 ccm. of glacial acetic acidand, with stirring and cooling, slowly nitrated with 100 ccm. of 40%solution of sodium nitrite added dropwise. The time taken for thedropwise addition is about 4 hours. The nitrating mixture is thenstirred for a further 10 hours. The oily nitro compound precipitatesfrom the yellow solution when water is added, and is absorbed inmethylene chloride. After the solution has been rendered neutral byshaking out with soda solution, the dried methylene chloride isevaporated. 33 g. of yellow, oily nitro compound remain behind, whichare absorbed in 170 ccm. of methanol and reduced catalytically in thepresence of Raney nickel. After it has been freed from the nickel, thereare immediately added to the colourless amine solution 200 ccm. offluoboric acid (3538% It is then, after evaporation of the methanol,diluted with 200 ccm. of water and filtered over animal charcoal. Whendiazotisation is effected with 50 ccm. of 2 N solution of sodiumnitrite, the diazo compound from l-N-(beta-hydroxyethyl-betaphenoxyethyl) amino 2 methoxy-4-aminobenzene precipitates in crystallineform and, for purification, is recrystallised from a littleisopropanol/water and then twice from water. Yellow crystals (yield: 15g.) are obtained. Melting point: C, With decomposition.

PREPARATION OF THE COMPOUND OF FORMULA (V) To the solution of 17.3 g. ofl-N-(beta-hydroxyethylbeta-phenoxyethyl)-amino 2,5 diethoxybenzene in140 ccm. of approximately 16% hydrochloric acid is added dropwise asolution of 4-nitrobenzenediazonium chloride in hydrochloric acid. Whenthe mixture is stirred and then stands in ice, a red dye precipitates inthe form of the hydrochloric acid salt. This is filtered with suctionand, for purification, recrystallised from glycolmonmethylether/ethanol.Yield: 21 g., melting point 190-191 C. By treatment of the dye withn-solution of caustic soda the dyes free base is obtained which iscatalytically reduced in methanolic solution in the presence of Raneynickel, filtered off from the nickel after reduction, and freed from thesolvent by evaporation. In order to remove p-phenylenediamine the oilyamine which remains behind is shaken with water and then distilled invacuo. Boiling point 241 C. (2 mm.). Yield of oily1-N-(betahydroxyethyl-beta-phenoxyethyl) amino 2,5 diethoxy-4-aminobenzenez 10 g. Of this compound, for diazotisation 6 g. aredissolved in com. of 16% hydrochloric acid, and 10 ccm. of 2 N solutionof sodium nitrite are added to it. The yellow solution obtained isfiltered over animal charcoal and the diazo compound precipitated byadding 5 ccm. of 50% solution of stannic chloride, filtered with suctionand, for purification, dissolved in 700 ccm. of water with the additionof a little hydrochloric acid and filtered over animal charcoal. When 90g. of sodium chloride and a few drops of stannic chloride solution areadded the yellow diazo compound precipitates again and this is filteredwith suction and dried. Yield: 5 g., melting point 102 C., withdecomposition. Discolouration occurs at 70 C.

PREPARATION OF THE COMPOUND OF FORMULA (VI) 20.25 g. ofl-N-(beta-hydroxyethyl-beta-phenylthioethyl)-amino-Z-methoxy-5-chlorobenzeneare dissolved in a mixture consisting of ccm. of 34% sulphuric acid and20 ccm. of glacial acetic acid, and nitrated by adding dropwise 2.75ccm. of nitric acid (1.52). Upon the addition of water to the nitrationmixture, the oily, yellow nitro compound is precipitated and this isseparated with the aid of methylene chloride. From the dried solutionthere remains after evaporation of the methylene chloride 24 g. of oily,yellow nitro compound. 20 g. of this are absorbed in 200 ccm. ofmethanol and reduced in the presence of Raney nickel. The reductionmixture is filtered off from the nickel and the solvent evaporated fromthe filtrate. For the diazotisation, the oilyl-N-(beta-hydroxyethyl-beta-phenylthioethyl)-amino 2 methoxy-4-amino-S-chlorobenzene is dissolved in 300 ccm. of approximately 8%hydrochloric acid. To this solution are added 20 ccm. of 2 N solution ofsodium nitrite. The yellow diazo solution obtained is filtered overanimal charcoal and the diazo compound precipitated out of the solutionby the addition of 10 ccm. of 50% solution of stannic chloride and 50 g.of sodium chloride. The diazo compound is then filtered with suctionand, for purification, dissolved in water and reprecipitated by addingsodium chloride. Yield: 10 g., melting point 9092 C., withdecomposition.

PREPARATION OF THE COMPOUND OF FORMULA (VII) 22.6 g. ofl-N-(beta-hydroxyethyl-beta-naphthoxyethyl)-amino-2-methoxy-5-chlorobenzene are dissolved in 300 ccm. ofglacial acetic acid and to this solution are added dropwise 50 ccm. of40% solution of sodium nitrite. The nitro compound, which precipitatesin oily form, is separated, freed from the glacial acetic acid byshaking with water and then reduced catalytically with Raney nickel in200 ccm. of ethanol. After the solution has been filtered oil from thenickel, the solvent is evaporated from it and thel-N-(beta-hydroxyethyl-betanaphthoxyethyl)-amino-2-methoXy-4-aminochlorobenzene which remains behind is, as crude product, absorbed in 300ccm. of 16% hydrocloric acid and diazotised by adding dropwise 20 ccm.of 2 N solution of sodium nitrite. When 5 ccm. of 50% solution of zincchloride are added, the diazo compound precipitates out of the yellowsolution as zinc chloride double salt, which is purified by dissolvingit in 700 ccm. of water and precipitating it with sodium chloride.Melting point: 100- 120 C., with decomposition.

PREPARATION OF THE COMPOUND OF FORMULA (VIII) 20.1 g. of1-N-(beta-hydroxyethyl-beta-phenoxypropyl)-amino-Z-methoxy-S-chlorobenzene are dissolved in 120 ccm. of 34%sulphuric acid and nitrated by dropwise addition of 2.75 ccm. of nitricacid (1.52). In the course of this being done the temperature rises from25 C. to 32 C. The initially oily nitro compound becomes solid (meltingpoint 8488 C.) during further stirring. It is filtered with suction anddissolved in 200 ccm. of methanol. By neutralisation of the solutionwith N solution of caustic soda, sodium sulphate is precipitated fromwhich the soluiton is filtered off and reduced catalytically with Raneynickel. After filtration from the nickel, the solvent is evaporated. Thel-N-(beta-hydroxyethyl-betaphenoxy-propyl)-amino 2methoxy-4-amino-S-chlorobenzene is dissolved in 250 ccm. of 35-38%fluoboric acid and diazotised with 25 ccm. of 2 N solution of sodiumnitrite. The initially oily diazo compound becomes solid during furtherstirring. It is filtered with suction and, for purification,recrystallised from 600 ccm. of water. The yellowish-orange colouredproduct has a melting point of 112-l14 C., with decomposition. Yield: 10g.

PREPARATION OF THE COMPOUND OF FORMULA (IX) By reaction of 30 g. ofbeta-phenoxyethyl-aniline (Clemo, Perkin Chem. Soc., London, volume 121,page 645) with propylene oxide, advantageously at an initial pressure of5 atmospheres gauge nitrogen, 3.3 g. of 1- N-(beta-hydroxypropyl-beta-phenoxyethyl)-aniline is obtained which boilsat 178-181 C. (1.5 mm.). 33 g. of this tertiary base are dissolved in 80ccm. of glycolmonomethylether and 250 ccm. of 30% sulphuric acid. Tothis solution 26.4 ccm. of 40% solution of sodium nitrite are addeddropwise at 10 C. in the course of one hour. The nitro compound formedremains in solution and is reduced by addng a total of 31 g. of Zincdust at 2530 C., with ice cooling. The colourless reduction solution isfiltered and then rendered strongly alkaline with 10 N solution ofcaustic soda. The l-N-(beta-hydroxypropyl-beta phenoxy- 8 PREPARATION OFTHE COMPOUND OF FORMULA (X) of methanol. The solution is renderedneutral with 10 N solution of caustic soda and filtered off from theprecipitated sodium sulphate. Raney nickel is added for the thecatalytic reduction of the nitro compound. After reduction, the solutionis filtered off from the nickel, the solvent evaporated and the oilyl-N-(beta-hydroxyethylbeta-4-chlorophenoxyethyl)amino-2-methoxy-4-amino- 5-chlorobenzene absorbed in 300 ccm. of 16%bydrochloric acid. Diazotisation of the last-named compound is eifectedby dropwise addition of 23 ccm. of 2 N solution of sidium nitrite. Thediazo compound precipitates out of the yellow solution when 5 ccm. of50% solution of stannic chloride are added. For purification it isreprecipitated by dissolving it in water and adding sodium chloride.Yield: 16 g. Melting point: C., with decomposition. Sintering occursaround 75 C.

PREPARATION OF THE COMPOUND OF FORMULA (X1) 107 g. of 2-toluidine areheated to the boil together with 60 ccm. of water and 0.5 g. of sodiumdiisobutylnaphthalenesulphonate. 110 g. of bromoethylphenylether areadded dropwise to the mixture in 2 hours, with stirring, and stirring iscontinued for a further 15 hours. The reaction mixture formed is twiceshaken out with water, with the addition of methylene chloride. Afterseparation of the aqueous layer, the solvent is evaporated from thereaction product and the oily residue which remains is distilled invacuo. The yield of 1-N-(beta-phenoxyethyl)- amino-2-methylbenzene is 70g., and the boiling point at 2 mm. pressure is 168-171 C.

35 g. of l-N-(beta-phenoxyethyl)-amino-2-methylbenzene together withccm. of methanol and 62 ccm. of ethylene hydroxide are heated for 4hours to 100 C. at an initial pressure of 5 atmospheres nitrogen in a /2litre rocking autoclave. The solvent is evaporated from the reactionmixture and the oily residue distilled in vacuo. The l-N-(beta-hydroxyenthyl-beta-phenoxyethyl)- amino-2-methylbenzene obtainedboils at -187 C. at a pressure of 2 mm. The yield is 36 g.

23 g. of the above-mentioned tertiary base are dissolved in 160 ccm. of16% hydrochloric acid and coupled to form a dye with diazotisedp-nitroaniline in the presence of pyridine. By catalytic reduction ofthe dye obtained, 1 N (beta-hydroxyethyl-beta-phenoxyethyl) amino-2-methyl-4-aminobenzene with a boiling point of 232- 234 C. at a pressureof 2 mm. is arrived at.

6 g. of this mono-tertiary diamine are dissolved in 100 ccm. of 16%hydrochloric acid and diazotised with 10 ccm. of 2 N solution of sodiumnitrite. The yellow diazo solution obtained is filtered over charcoaland 4 g. of cadmium chloride are added to it. The diazo compoundseparates in greasy form and, for purification, is filtered as aqueoussolution over charcoal and precipitated with sodium chloride. Thecrystals melt at 155l57 C., with decomposition.

The diazo compounds of the present invention may be used in the normalmanner as diazo components of diazotype compositions and diazotypematerial prepared therewith. Numerous available azo coupler componentsmay be used to prepare developer solutions normally employed withone-component diazotype materials. The following examples set forth afew embodiments of the present invention.

beta-hydroxyethyl-beta-phenoxyethyl) amino 2- hydroxylethoxy4-amino-5-chlorobenzene (Formula III) 1.8

and dried. After exposure of the sensitised paper under an original, asolution of Trisodium citrate 4.0 Trisodium phosphate 2.0 Borax 2.0Phloroglucinol 0.6 Resorcinol 0.6 Sodiumdiisopropylnaphthalenesulphonate 0.1

in 100 ccm. of water is applied as a thin coating, approximately 10-15g./m. A copy is obtained which shows strong, brown lines on a Whitebackground.

EXAMPLE 2 Transparent paper is coated with an aqueous solution which foreach 90 ccm. of water contains:

Citric acid g 0.5 Sodium 1,3,6--naphthalenetrisulphonate g 3.5 Fluoboricacid salt of the diazo compound from 1 N (beta hydroxyethyl betaphenoxyethyl)- amino 2 methoxy 4 aminobenzene (Formula IV) g 3.2Triglycol ccm 2.5 Isopropanol ccm 5.0

and, dried. After exposure of the sensitised paper under an original thelatent image which is formed is developed with the solution stated inExample 1 containing phloroglucinol and resorcinol. Copies with darkbrown lines on a transparent background are obtained. The copies aresuitable as intermediate originals for further photocopying.

, EXAMPLE 3 White photocopying base paper with a precoat consisting ofcolloidal silicic acid and polyvinyl acetate is coated with an aqueoussolution which in 95 ccm. of water contains:

Tartaric acid g 0.5 Sodium 1,3,6-naphthalenetrisulphonate g 3.5 Saponing 0.02 Fluoboric acid salt of the diazo compound from 1- N (betahydroxyethyl-beta-phenoxyethyl)-amino 2 methoxy-4-amino-5-chloro-benzene(Formula I) g 1.8 Zinc chloride double salt of the diazo compound from1- (4-rnethylphenyl -mercapto-2,5-diethoxy- 4-aminobenzene g 0.2Isopropanol ccm 5.0

The dried, sensitised paper, after exposure under an original, isdeveloped with a solution of:

Sodium benzoate 2.4 Sodium adipate 2.0 Trisodium citrate 9.0 Adipic acid0.2 Sodium chloride 5 .0

Phloroglucinol 0.35

in 100 ccm. of water, Photocopies with deep black lines on a whitebackground are obtained.

10 The same result is obtained with the fluoboric acid salt of the diazocompound froml-N-(beta-hydroxyethylbeta-phenoxyethyl)amino-2-ethoxy-4-amino 5chlorobenzene (Formula II).

EXAMPLE 4 White photocopying base paper, which is provided with aprecoat consisting of colloidal silicic acid and polyvinyl acetate, iscoated with an aqueous solution which for each com. of water contains:

Sodium 1,3,6-naphthalenetrisulphonate g 4.0 Citric acid g 0.5

Of the diazo compound froml-N-(beta-hydroxyethyl-beta-phenoxyethyl)-arnino 2,5 diethoxy-4-aminobenzene (Formula V) in the form of its double salt with stannicchloride g 1.8 Isopropanol ccm 5.0

and dried. The paper, exposed under an original, is treated with thealkaline developer solution described in Example 1 containingphloroglucinol and resorcinol. A copy with very dark brown lines on awhite background is obtained.

EXAMPLE 5 White photocopying base paper as used in Example 4 with aprecoat of colloidal silicic acid and polyvinyl acetate is coated withan aqueous solution which contains for each 95 ccm, of water:

Sodium 1,3,6-naphthalenetrisulphonate g 4.0

Citric acid and g 0.5

Stannic chloride double salt of the diazo compound from 1 N(beta-hydroxyethyl-beta-phenylthioethyl)-amino-2-methoxy-4-amino 5chlorobenzene (Formula VI) g 1.8 Isopropanol ccm 5.0

and dried. The paper, exposed under an original, is developed with thedeveloper solution stated in Example 3. A copy with blue-black lines ona white background is obtained.

EXAMPLE 6 White photocopying base paper, which is provided with aprecoat consisting of colloidal silicic acid and polyvinyl acetate, iscoated with an aqueous solution which for each 95 ccm. of watercontains:

Citric acid g 4.0

Zinc chloride double salt of the diazo compound from 1 N(beta-hydroxyethyl-beta-naphthoxyethyl)-amino 2methoxy-5-chloro-4-aminoben- Zene (Formula VII) g 2.0

Isopropanol ccm 5.0

and dried, The paper, exposed under an original, is developed with thedeveloper solution used in Example 3. A copy with blue-black lines on awhite background is obtained.

If the developer solution described in Example 1, containingphloroglucinol and resorcinol, is used for the development of theexposed paper, a copy with very dark brown lines is obtained.

Equal results are obtained with photocopying paper which is preparedwith the use (as light-sensitive substance) of the compounds withFormula VIII (borofluoride of the diazo compound froml-N-(beta-hydroxyethyl-beta-phenoxypropyl-amino-2-methoxy 5 chloro-4-aminobenzene) or Formula IX, (stannic chloride double salt of thediazo compound froml-N-(beta-hydroxypropyl-beta-phenoxyethyl)-amino-4-aminobenzene) orFormula XI (cadmium chloride double salt of the diazo compound froml-N-(beta-hydroxyethyl-beta-phenoxyethyl)-amino-2-methyl-4-aminobenzene) EXAMPLE 7 V A white photocopying basepaper loaded with baryta is coated with an aqueous solution whichcontains for each 95 ccm. of water:

Citric acid g 4.0

Stannic chloride double salt of the diazo compound from 1 N(beta-hydroxyethyl-beta-chloro-phenoxyethyl) amino-2-methoxy-chloro-4-aminobenzene (Formula X) g 2.5

Isopropanol ccm 5.0

and dried. From the paper, after it has been exposed under an originaland developed with the developer described in Example 3 containingphloroglucinol, a copy with blue-black lines is obtained.

The foregoing examples have been presented for the purpose ofillustration and should not be taken to limit the invention. It will beapparent that the described examples are capable of many variations andmodifications which are likewise to be included within the scope of thepresent invention as set forth in the appended claims.

What is claimed is:

1. Diazotype material comprising a support and a light-Sensitivecomposition thereon comprising a lightsensitive diazonium componenthaving the general formula:

wherein:

R is a hydroxyalkyl of 2 or 3 carbon atoms;

R is an aryloxalkyl or arylthioalkyl wherein the alkyl contains 2 or 3carbon atoms;

R; is hydrogen, methyl, methoxy, ethoxy, or beta-hydroxy-ethoxy;

R is hydrogen, chlorine, or ethoxy; and

X is an anion of an acid.

2. Material according to claim 1 wherein said diazo component is 2chloro 4-(N-B-hydroxyethyl-N-fl-phenoxyethyl) amino 5 methoxybenzene-diazoniumborofluoride.

3. Material according to claim 1 wherein said diazo component is 2chloro 4 (N-fi-hydroxyethyl-N-fiphenoxyethyl) amino 5 ethoxy benzenediazoniumborofluoride.

4. Material according to claim 1 wherein said diazo component is 2chloro 4 (N-fl-hydroxyethyl-N-[S- phenoxyethyl) amino 5 hydroxyethoxybenzenediazonium borofiuoride.

5. Material according to claim 1 wherein said diazo component is 4 (N ,8hydroxyethyl-N-fi-phenoxyethyl) amino 5 methoxy benzenediazonium-borofluoride.

6. Material according to claim 1 wherein said diazo component is 2,5diethoxy 4 (N-B-hydroxyethyl-N-B- phenoxyethyl) amino benzene diazoniumchloride- 811014.

7. Material according to claim 1 whereinsaid diazo component is 2 chloro4 (N f3 hydroxyethyl-N-fiphenylthioethyl) amino 5 methoxybenzenediazonium-chloride- SnCl 8. Material according to claim 1 whereinsaid diazo component is 2 chloro 4 (N-B-hydroxyethyl-N-B-naphthoxyethyl) amino 5 methoxy benzene diazonium-chloride ZnCl 2.

9. Material according to claim 1 wherein said diazo component is 2chloro 4 (N-fi-hydroxyethyl-N-yphenoxypropyl) aminoS-methoxy-benzene-diazoniumborofluoride.

10. Material according to claim 1 wherein said diazo component is4-(N-fl-hydroxypropyl-N-fi-phenoxyethyl)-amino-benzene-diazonium-chloride-SnCl 11. Material according to claim 1wherein said diazo component is 2 chloro 4-(N-fl-hydroxyethyl-N-fi-4'-chloro phenoxyethyl) amino 5 methoxy-benzenediazonium-chloride SnCl 12.Material according to claim 1 wherein said diazo component is 3methyl-4-(N-fi-hydroxyethyl-N-fi-phenoxyethyl)amino-benzene-diazonium-chloride-CdCl 2.

13. Diazonium salt having the general formula:

wherein R is a hydroxyalkyl of 2 or 3 carbon atoms;

R is an aryloxyalkyl or arylthioalkyl wherein the alkyl contains 2 or 3carbon atoms;

R is hydrogen, methyl, methoxy, ethoxy, or beta-hydroxy-ethoxy;

R is hydrogen, chlorine, or ethoxy; and

X is an anion of an acid.

14. Diazonium salt according to the formula in claim 13, wherein:

R is beta-hydroxyethyl,

R is beta-phenoxyethyl or gamma-phenoxypropyl,

R is methoxy or ethoxy,

R is H or Cl, and

X is the anion of fluoboric acid or the chloride ion in double saltcombination with stannic chloride.

References Cited UNITED STATES PATENTS 2,529,464 11/1950 Von Glahn eta1. 969l 2,833,649 5/1958 Sus et a1. 9691 3,294,541 12/1966 Werner etal. 9691 FOREIGN PATENTS 711,390 6/1954 Great Britain. 867,630 5/ 1961Great Britain.

OTHER REFERENCES Vander Grinten Bulletin, December 1962, pp. 1-7 reliedon.

NORMAN G. TORCHIN, Primary Examiner C. BOWERS, Assistant Examiner US.Cl. X.R.

